KR102295297B1 - High molecular compound for electro-conductive polymer and process for producing same - Google Patents

High molecular compound for electro-conductive polymer and process for producing same Download PDF

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KR102295297B1
KR102295297B1 KR1020180019814A KR20180019814A KR102295297B1 KR 102295297 B1 KR102295297 B1 KR 102295297B1 KR 1020180019814 A KR1020180019814 A KR 1020180019814A KR 20180019814 A KR20180019814 A KR 20180019814A KR 102295297 B1 KR102295297 B1 KR 102295297B1
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carbon atoms
repeating unit
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dopant
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준 하타케야마
다카유키 후지와라
고지 하세가와
다카유키 나가사와
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신에쓰 가가꾸 고교 가부시끼가이샤
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Abstract

[과제] 유기 용제에 가용이며, 연료 전지용이나 도전성 재료용의 도펀트로서 적합하게 이용되는 도전성 폴리머용 고분자 화합물을 제공한다.
[해결수단] 하기 화학식(1)로 표시되는 반복 단위 a를 1종 이상 포함하고, 중량 평균 분자량이 1,000∼500,000의 범위인 것인 도전성 폴리머용 고분자 화합물.

Figure 112018017704619-pat00041

(식 중, R1은 수소 원자 또는 메틸기이고, Rf1은 탄소수 1∼4의 직쇄상, 분기상의 알킬기, 또는 페닐기이며, Rf1 중에 1개 이상의 불소 원자 또는 트라이플루오로메틸기를 갖는다. Z1은 단일 결합, 탄소수 6∼12의 아릴렌기, 또는 -C(=O)-O-R2-이고, R2는 탄소수 1∼12의 직쇄상, 분기상, 환상의 알킬렌기, 탄소수 6∼10의 아릴렌기, 또는 탄소수 2∼10의 알켄일렌기이며, R2 중에 에터기, 카보닐기, 에스터기를 갖고 있어도 된다. a는 0＜a≤1.0이다.)[Problem] To provide a polymer compound for conductive polymers that is soluble in organic solvents and is suitably used as a dopant for fuel cells or conductive materials.
[Solutions] A polymer compound for conductive polymers comprising at least one repeating unit a represented by the following formula (1) and having a weight average molecular weight in the range of 1,000 to 500,000.
Figure 112018017704619-pat00041

(Wherein, R 1 is a hydrogen atom or a methyl group, Rf 1 is a linear or branched alkyl group having 1 to 4 carbon atoms, or a phenyl group, and has at least one fluorine atom or a trifluoromethyl group in Rf 1 . Z 1 is a single bond, an arylene group having 6 to 12 carbon atoms, or -C(=O)-OR 2 -, and R 2 is a linear, branched, cyclic alkylene group having 1 to 12 carbon atoms, aryl having 6 to 10 carbon atoms It is a lene group or an alkenylene group having 2 to 10 carbon atoms, and may have an ether group, a carbonyl group, or an ester group in R 2 , where a is 0<a≤1.0.)

Description

도전성 폴리머용 고분자 화합물 및 그의 제조 방법{HIGH MOLECULAR COMPOUND FOR ELECTRO-CONDUCTIVE POLYMER AND PROCESS FOR PRODUCING SAME}The polymer compound for conductive polymers, and its manufacturing method TECHNICAL FIELD

본 발명은, 도전성 폴리머용 고분자 화합물 및 그의 제조 방법에 관한 것이다.The present invention relates to a polymer compound for conductive polymers and a method for producing the same.

연료 전지나 도전성 고분자의 도펀트 폴리머로서 설포기 함유 폴리머가 이용되고 있다. 연료 전지용으로서는, 등록상표 나피온으로 대표되는 바이닐퍼플루오로알킬에터설폰산, 도전성 고분자용의 도펀트 폴리머로서는, 바이닐설폰산이나 스타이렌설폰산의 중합체가 널리 이용되고 있다(특허문헌 1). 또한, 특허문헌 2에서는, 도펀트 폴리머로서 양성자가 양이온으로 치환된 불소화산 폴리머가 제안되어 있고, 이 중에서 비스플루오로알킬설폰일이미드의 리튬염을 갖는 스타이렌 유도체의 도펀트가 나타나 있다.A sulfo group-containing polymer is used as a dopant polymer for a fuel cell or a conductive polymer. For fuel cells, vinyl perfluoroalkyl ethersulfonic acid typified by registered trademark Nafion, and as a dopant polymer for conductive polymers, vinylsulfonic acid and styrenesulfonic acid polymers are widely used (Patent Document 1). Further, Patent Document 2 proposes a fluorinated acid polymer in which a proton is substituted with a cation as a dopant polymer, and among these, a dopant of a styrene derivative having a lithium salt of bisfluoroalkylsulfonylimide is disclosed.

바이닐퍼플루오로알킬에터설폰산은 화학적으로는 안정성이 높아 내구성이 우수하지만, 유리 전이점이 낮아, 이것을 이용한 연료 전지가 고온에 노출되면 폴리머가 열 플로를 일으켜 이온 전도성이 저하되어 버리는 문제가 있다. 또한, 비스플루오로알킬설폰일이미드를 갖는 스타이렌 유도체도 마찬가지의 문제를 갖는다. 이온 전도성을 높이려면, α위가 불소화된 설포기로 대표되는 초강산 폴리머가 유효하지만, 이것에 수반하여 유리 전이점이 높고 화학적으로도 안정된 재료는 발견되지 않았다.Vinyl perfluoroalkylethersulfonic acid has high chemical stability and excellent durability, but has a low glass transition point, so that when a fuel cell using the same is exposed to high temperatures, the polymer causes thermal flow, thereby reducing ionic conductivity. Further, a styrene derivative having a bisfluoroalkylsulfonylimide has a similar problem. In order to increase the ionic conductivity, a super acid polymer represented by a sulfo group in which the α-position is fluorinated is effective, but a material with a high glass transition point and chemical stability has not been found.

또한, 폴리싸이오펜, 폴리아닐린, 폴리피롤 등의 공액 이중 결합을 갖는 도전성 고분자는, 이것 자체는 도전성을 나타내지 않지만, 설폰산 등의 강산을 도핑하는 것에 의해 도전성이 발현된다. 도펀트로서는 폴리스타이렌설폰산(PSS)이 가장 잘 이용되고 있다. 이것은, PSS의 도핑에 의해 도전율이 가장 높아지기 때문이다.In addition, conductive polymers having a conjugated double bond, such as polythiophene, polyaniline, or polypyrrole, do not exhibit conductivity by themselves, but exhibit conductivity by doping with a strong acid such as sulfonic acid. As the dopant, polystyrene sulfonic acid (PSS) is best used. This is because the conductivity is highest by doping of PSS.

PSS는 수용성 수지이며, 유기 용제에는 거의 용해되지 않는다. 따라서, PSS를 도펀트로 한 폴리싸이오펜도 수용성이다.PSS is a water-soluble resin and hardly dissolves in organic solvents. Therefore, polythiophene using PSS as a dopant is also water-soluble.

PSS를 도펀트로 한 폴리싸이오펜은 고도전성이고 또한 고투명하기 때문에 ITO(인듐-주석 산화물)를 대체하는 유기 EL 조명용의 도전막으로서 기대되고 있다. 그렇지만 유기 EL의 발광체는, 수분에 의해 화학 변화되어 발광하지 않게 된다. 즉, 수용성 수지의 도전막을 유기 EL에 이용하면, 수지가 물을 포함하기 때문에 유기 EL의 발광 수명이 짧아져 버린다고 하는 문제가 있다.Polythiophene using PSS as a dopant is highly conductive and highly transparent, so it is expected as a conductive film for organic EL lighting replacing ITO (indium-tin oxide). However, the organic EL light-emitting body is chemically changed by moisture, so that it does not emit light. That is, when the conductive film of a water-soluble resin is used for organic electroluminescent, since resin contains water, there exists a problem that the light emission lifetime of organic electroluminescent will become short.

일본 특허공개 2008-146913호 공보Japanese Patent Laid-Open No. 2008-146913 일본 특허 제5264723호Japanese Patent No. 5264723

본 발명은 상기 사정에 비추어 이루어진 것으로, 유기 용제에 가용이며, 연료 전지용이나 도전성 재료용의 도펀트로서 적합하게 이용되는 도전성 폴리머용 고분자 화합물을 제공하는 것을 목적으로 한다. 또한, 이와 같은 도전성 폴리머용 고분자 화합물의 제조 방법을 제공하는 것을 목적으로 한다.The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polymer compound for conductive polymers that is soluble in organic solvents and is suitably used as a dopant for fuel cells and conductive materials. Another object of the present invention is to provide a method for producing such a polymer compound for conductive polymers.

상기 과제를 해결하기 위해서, 본 발명에서는, 도전성 폴리머용 고분자 화합물로서, 하기 화학식(1)로 표시되는 반복 단위 a를 1종 이상 포함하고, 중량 평균 분자량이 1,000∼500,000의 범위인 것인 도전성 폴리머용 고분자 화합물을 제공한다.In order to solve the above problems, in the present invention, a conductive polymer comprising one or more repeating units a represented by the following formula (1) as a polymer compound for conductive polymers and having a weight average molecular weight in the range of 1,000 to 500,000 high molecular weight compounds for

Figure 112018017704619-pat00001
Figure 112018017704619-pat00001

(식 중, R1은 수소 원자 또는 메틸기이고, Rf1은 탄소수 1∼4의 직쇄상, 분기상의 알킬기, 또는 페닐기이며, Rf1 중에 1개 이상의 불소 원자 또는 트라이플루오로메틸기를 갖는다. Z1은 단일 결합, 탄소수 6∼12의 아릴렌기, 또는 -C(=O)-O-R2-이고, R2는 탄소수 1∼12의 직쇄상, 분기상, 환상의 알킬렌기, 탄소수 6∼10의 아릴렌기, 또는 탄소수 2∼10의 알켄일렌기이며, R2 중에 에터기, 카보닐기, 에스터기를 갖고 있어도 된다. a는 0＜a≤1.0이다.)(Wherein, R 1 is a hydrogen atom or a methyl group, Rf 1 is a linear or branched alkyl group having 1 to 4 carbon atoms, or a phenyl group, and has at least one fluorine atom or a trifluoromethyl group in Rf 1 . Z 1 is a single bond, an arylene group having 6 to 12 carbon atoms, or -C(=O)-OR 2 -, and R 2 is a linear, branched, cyclic alkylene group having 1 to 12 carbon atoms, aryl having 6 to 10 carbon atoms It is a lene group or an alkenylene group having 2 to 10 carbon atoms, and may have an ether group, a carbonyl group, or an ester group in R 2 , where a is 0<a≤1.0.)

이와 같은 도전성 폴리머용 고분자 화합물이면, 유기 용제에 가용이며, 연료 전지용이나 도전성 재료용의 도펀트로서 적합하게 이용되는 특정한 강산의 설폰아마이드기를 갖는 도전성 폴리머용 고분자 화합물이 된다.Such a high molecular compound for conductive polymers is soluble in organic solvents, and it becomes a high molecular compound for conductive polymers having a sulfonamide group of a specific strong acid that is suitably used as a dopant for fuel cells or conductive materials.

이 때, 상기 도전성 폴리머용 고분자 화합물이, 추가로 하기 화학식(2)로 표시되는 반복 단위 b를 갖는 것인 것이 바람직하다.At this time, it is preferable that the said polymer compound for conductive polymers has a repeating unit b further represented by following formula (2).

Figure 112018017704619-pat00002
Figure 112018017704619-pat00002

(식 중, b는 0＜b＜1.0이다.)(Wherein, b is 0<b<1.0.)

상기 반복 단위 a가, 폴리스타이렌설폰산의 반복 단위 b와 공중합된 것이면, 도전성이 높은 도펀트 폴리머로서 이용할 수 있다.If the repeating unit a is copolymerized with the repeating unit b of polystyrenesulfonic acid, it can be used as a dopant polymer having high conductivity.

또한 이 때, 상기 화학식(1)로 표시되는 반복 단위 a가, 하기 화학식(3)으로 표시되는 반복 단위 a1∼a4로부터 선택되는 1종 이상을 포함하는 것인 것이 바람직하다.Further, in this case, it is preferable that the repeating unit a represented by the formula (1) includes at least one selected from the repeating units a 1 to a 4 represented by the following formula (3).

Figure 112018017704619-pat00003
Figure 112018017704619-pat00003

(식 중, R1 및 Rf1은 상기와 마찬가지이다. a1, a2, a3, 및 a4는 0≤a1≤1.0, 0≤a2≤1.0, 0≤a3≤1.0, 0≤a4≤1.0, 0＜a1＋a2＋a3＋a4≤1.0이다.)(Wherein, R 1 and Rf 1 are the same as above. a 1 , a 2 , a 3 , and a 4 are 0≤a 1 ≤1.0, 0≤a 2 ≤1.0, 0≤a 3 ≤1.0, 0 ≤a 4 ≤1.0, 0<a 1 +a 2 +a 3 +a 4 ≤1.0)

이와 같은 반복 단위이면, 연료 전지용이나 도전성 재료용의 도펀트로서 더욱 적합한 것이 된다.Such a repeating unit is more suitable as a dopant for fuel cells or conductive materials.

더욱이, 본 발명에서는, 도전성 폴리머용 고분자 화합물의 제조 방법으로서, 카보닐기에 결합한 설폰아마이드기와 리튬, 나트륨, 칼륨, 또는 질소 화합물로 이루어지는 염의 구조를 갖는 모노머를 이용하여 중합 반응을 행하고, 중합 후, 이온 교환에 의해, 상기 카보닐기에 결합한 설폰아마이드기와 리튬, 나트륨, 칼륨, 또는 질소 화합물로 이루어지는 염의 구조를 카보닐기에 결합한 설폰아마이드기로 변환하는 것에 의해, 하기 화학식(1)로 표시되는 반복 단위 a를 포함하는 도전성 폴리머용 고분자 화합물을 제조하는 도전성 폴리머용 고분자 화합물의 제조 방법을 제공한다.Furthermore, in the present invention, as a method for producing a polymer compound for a conductive polymer, a polymerization reaction is carried out using a monomer having a salt structure comprising a sulfonamide group bonded to a carbonyl group and lithium, sodium, potassium, or a nitrogen compound, and after polymerization, By ion exchange, the structure of a salt consisting of a sulfonamide group bonded to the carbonyl group and lithium, sodium, potassium, or nitrogen compound is converted to a sulfonamide group bonded to a carbonyl group, whereby a repeating unit a represented by the following formula (1) It provides a method for producing a polymer compound for a conductive polymer for producing a polymer compound for a conductive polymer comprising:

Figure 112018017704619-pat00004
Figure 112018017704619-pat00004

(식 중, R1은 수소 원자 또는 메틸기이고, Rf1은 탄소수 1∼4의 직쇄상, 분기상의 알킬기, 또는 페닐기이며, Rf1 중에 1개 이상의 불소 원자 또는 트라이플루오로메틸기를 갖는다. Z1은 단일 결합, 탄소수 6∼12의 아릴렌기, 또는 -C(=O)-O-R2-이고, R2는 탄소수 1∼12의 직쇄상, 분기상, 환상의 알킬렌기, 탄소수 6∼10의 아릴렌기, 또는 탄소수 2∼10의 알켄일렌기이며, R2 중에 에터기, 카보닐기, 에스터기를 갖고 있어도 된다. a는 0＜a≤1.0이다.)(Wherein, R 1 is a hydrogen atom or a methyl group, Rf 1 is a linear or branched alkyl group having 1 to 4 carbon atoms, or a phenyl group, and has at least one fluorine atom or a trifluoromethyl group in Rf 1 . Z 1 is a single bond, an arylene group having 6 to 12 carbon atoms, or -C(=O)-OR 2 -, and R 2 is a linear, branched, cyclic alkylene group having 1 to 12 carbon atoms, aryl having 6 to 10 carbon atoms It is a lene group or an alkenylene group having 2 to 10 carbon atoms, and may have an ether group, a carbonyl group, or an ester group in R 2 , where a is 0<a≤1.0.)

이와 같은 제조 방법이면, 상기 화학식(1)로 표시되는 반복 단위 a를 포함하는 도전성 폴리머용 고분자 화합물을 용이하게 제조할 수 있다.According to such a manufacturing method, the polymer compound for conductive polymers containing the repeating unit a represented by the said Formula (1) can be manufactured easily.

또한 이 때, 상기 카보닐기에 결합한 설폰아마이드기와 리튬, 나트륨, 칼륨, 또는 질소 화합물로 이루어지는 염의 구조를 갖는 모노머를 이용하여 중합 반응을 행하여 얻어진 중합체가, 하기 화학식(4)로 표시되는 반복 단위를 포함하는 것인 것이 바람직하다.In addition, at this time, the polymer obtained by carrying out the polymerization reaction using a monomer having a salt structure consisting of a sulfonamide group bonded to the carbonyl group and lithium, sodium, potassium, or a nitrogen compound is a repeating unit represented by the following formula (4) It is preferable to include.

Figure 112018017704619-pat00005
Figure 112018017704619-pat00005

(식 중, R1, Z1, Rf1, 및 a는 상기와 마찬가지이고, X는 리튬, 나트륨, 칼륨, 또는 하기 화학식(5)로 표시되는 질소 화합물이다.)(Wherein, R 1 , Z 1 , Rf 1 , and a are the same as above, and X is lithium, sodium, potassium, or a nitrogen compound represented by the following formula (5).)

Figure 112018017704619-pat00006
Figure 112018017704619-pat00006

(식 중, R101d, R101e, R101f, 및 R101g는, 각각 수소 원자, 혹은 탄소수 1∼12의 직쇄상, 분기상 또는 환상의 알킬기, 알켄일기, 옥소알킬기 또는 옥소알켄일기, 탄소수 6∼20의 아릴기, 또는 탄소수 7∼12의 아르알킬기 또는 아릴옥소알킬기를 나타내고, 이들 기의 수소 원자의 일부 또는 전부가 알콕시기에 의해 치환되어 있어도 된다. R101d와 R101e, R101d와 R101e와 R101f는 환을 형성해도 되고, 환을 형성하는 경우에는, R101d와 R101e 및 R101d와 R101e와 R101f는 탄소수 3∼10의 알킬렌기, 또는 식 중의 질소 원자를 환 중에 갖는 헤테로방향족환을 나타낸다.)(Wherein, R 101d , R 101e , R 101f , and R 101g are each a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, and 6 carbon atoms represents an aryl group of -20, an aralkyl group of 7 to 12 carbon atoms, or an aryloxoalkyl group, and some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group.R 101d and R 101e , R 101d and R 101e and R 101f may form a ring, and in the case of forming a ring, R 101d and R 101e and R 101d and R 101e and R 101f are an alkylene group having 3 to 10 carbon atoms, or a heterocyclic group having a nitrogen atom in the ring. represents an aromatic ring.)

이와 같은 반복 단위이면, 이온 교환에 의해 용이하게 상기 화학식(1)로 표시되는 반복 단위 a로 변환된다.If it is such a repeating unit, it is easily converted into the repeating unit a represented by the said Formula (1) by ion exchange.

이상과 같이, 본 발명의 도전성 폴리머용 고분자 화합물이면, 유기 용제에 가용이며, 연료 전지용이나 도전성 재료용의 도펀트로서 적합하게 이용되는 특정한 강산의 설폰아마이드기를 갖는 도전성 폴리머용 고분자 화합물이 된다.As described above, if the polymer compound for a conductive polymer of the present invention is soluble in an organic solvent, the polymer compound for a conductive polymer having a sulfonamide group of a specific strong acid is suitably used as a dopant for fuel cells or conductive materials.

이 도전성 폴리머용 고분자 화합물을 연료 전지에 이용하는 것에 의해, 고유전율인 연료 전지용 재료를 형성할 수 있다. 또한, 공액 이중 결합 폴리머용의 도펀트로서 이용하는 것에 의해, 고투명, 고도전성이고 내구성이 높은 도전막을 형성하는 것이 가능해진다. 또한, 본 발명의 도전성 폴리머용 고분자 화합물은 특정한 설폰아마이드기를 갖고 있다. 이 설폰아마이드기는, 편측에 불소화된 알킬기나 페닐기가 결합한 설폰기를 갖고, 다른 편측에 카보닐기를 갖는 구조가 되어 있다. 양측의 기의 전자 흡인 효과에 의해, 이 설폰아마이드기의 산성도는, 편측에만 플루오로알킬기가 결합한 설폰기를 갖는 설폰아마이드보다는 높아지고, α위가 불소화된 설폰산보다는 낮아진다. 도펀트 폴리머의 산성도가 높으면, 강산에 의한 강한 이온 결합에 의해, 도펀트로서의 능력이 높고, 이온으로서의 안정성이 높으며, 발광 효율이 높은 것이 된다. 한편, 도펀트 폴리머의 산성도가 지나치게 높으면, 유기 EL로서의 발광 수명이 짧아진다. 이것은, 발광 중에 산이 발광층으로 이동하여, 발광체가 되는 금속의 리간드와 교환 반응을 일으키기 때문이라고 생각된다. 본 발명의 도전성 폴리머용 고분자 화합물과 공액 이중 결합의 폴리머의 복합체를 적용하는 것에 의해, 유기 EL의 고효율과 고수명의 양방을 달성할 수 있다.By using this polymer compound for conductive polymers in a fuel cell, a fuel cell material having a high dielectric constant can be formed. Moreover, by using it as a dopant for conjugated double bond polymers, it becomes possible to form a highly transparent, highly conductive, and durable electrically conductive film. Moreover, the high molecular compound for conductive polymers of this invention has a specific sulfonamide group. This sulfonamide group has a structure having a sulfone group bonded to a fluorinated alkyl group or a phenyl group on one side and a carbonyl group on the other side. Due to the electron-withdrawing effect of the groups on both sides, the acidity of this sulfonamide group is higher than that of a sulfonamide having a sulfone group to which a fluoroalkyl group is bonded only on one side, and lower than that of a sulfonic acid in which the α-position is fluorinated. When the acidity of the dopant polymer is high, the ability as a dopant is high due to the strong ionic bond by the strong acid, the stability as an ion is high, and the luminous efficiency is high. On the other hand, when the acidity of the dopant polymer is too high, the emission lifetime as organic EL becomes short. This is considered to be because the acid moves to the light emitting layer during light emission to cause an exchange reaction with a metal ligand serving as a light emitting body. By applying the composite of the polymer compound for conductive polymers of the present invention and a polymer having a conjugated double bond, both high efficiency and long life of organic EL can be achieved.

또한, 본 발명의 제조 방법이면, 이와 같은 본 발명의 도전성 폴리머용 고분자 화합물을 용이하게 제조할 수 있다.Moreover, if it is the manufacturing method of this invention, such a high molecular compound for conductive polymers of this invention can be manufactured easily.

전술한 바와 같이, 유기 용제에 가용이며, 연료 전지용이나 도전성 재료용의 도펀트로서 적합하게 이용되는 도전성 폴리머용 고분자 화합물의 개발이 요구되고 있었다.As described above, there has been a demand for the development of a polymer compound for conductive polymers that is soluble in organic solvents and is suitably used as a dopant for fuel cells or conductive materials.

본 발명자들은, 유기 EL의 소자의 열화를 초래하는 물을 함유하는 수용성의 도전성 폴리머를, 수분 함유율이 극히 적은 유기 용제 가용형으로 하여 소자 열화를 방지하기 위해서, 수용성이고 유기 용제로의 용해성이 부족한 도펀트인 폴리스타이렌설폰산으로부터, 유기 용제로의 용해성이 높은 도펀트용의 폴리머의 개발을 시도했다. 유기 용제로의 용해성을 높이려면 장쇄 알킬기나 불소 원자의 도입이 효과적이므로 불소 원자의 도입을 검토했지만, 장쇄 알킬기나 과잉한 불소 원자의 도입은 도전율의 저하를 초래하므로 바람직하지 않음이 판명되었기 때문에, 적은 불소 원자의 도입에 의한 강산성 유닛의 구축을 목표로 했다. 전술한 비스플루오로알킬설폰일이미드는 높은 산성도를 갖지만, 양측에 플루오로알킬기를 갖기 때문에, 이것을 도펀트 폴리머에 적용했을 때의 도전율은 낮다. 그래서, 본 발명자들은, 비스플루오로알킬설폰일이미드에 있어서의 편측의 플루오로알킬설폰일기를 카보닐기로 변경한 바, 카보닐기의 전자 흡인성에 의해 적은 불소 원자로 충분히 높은 산성도를 갖는 설폰아마이드기를 얻을 수 있었다.The present inventors, in order to prevent device deterioration by making a water-soluble conductive polymer containing water, which causes deterioration of an organic EL element, into an organic solvent-soluble type having an extremely low water content, it is water-soluble and lacks solubility in an organic solvent. From polystyrene sulfonic acid, which is a dopant, an attempt was made to develop a polymer for a dopant with high solubility in an organic solvent. In order to increase solubility in organic solvents, introduction of a long-chain alkyl group or a fluorine atom is effective, so the introduction of a fluorine atom has been considered. It aimed to construct a strongly acidic unit by introducing a small number of fluorine atoms. Although the above-mentioned bisfluoroalkylsulfonylimide has high acidity, since it has fluoroalkyl groups on both sides, the electrical conductivity when it is applied to a dopant polymer is low. Therefore, the present inventors have changed the fluoroalkylsulfonyl group on one side of the bisfluoroalkylsulfonylimide to a carbonyl group. Due to the electron withdrawing property of the carbonyl group, a sulfonamide group having sufficiently high acidity with few fluorine atoms could get

도펀트 폴리머는, 공액 이중 결합의 폴리머와 복합체를 형성하여, 공액 이중 결합 폴리머의 일부를 이온화하는 것에 의해 도전성이 향상된다. 도펀트 폴리머의 산성도가 높을수록 공액 이중 결합 폴리머를 이온화할 수 있어, 유기 EL의 발광 효율이 향상된다.A dopant polymer forms a complex with the polymer of a conjugated double bond, and electroconductivity improves by ionizing a part of a conjugated double bond polymer. As the acidity of the dopant polymer is higher, the conjugated double bond polymer can be ionized and the luminous efficiency of organic EL is improved.

한편, 유기 EL의 발광 시의 광도 저하를 막기 위해서, 수명 열화의 원인이 되는 과도한 산성 상태를 완화시키는 것이 필요하다. α위가 불소화된 설폰산이나 비스플루오로알킬설폰일이미드는 초강산이기 때문에, 발광 시에 도전성 폴리머가 적용되는 양극층으로부터 발광층으로 양성자 이동이 일어나고, 이것에 의해 발광 효율이 저하되어 광도가 저하된다. 이것을 방지하려면 도펀트 폴리머의 산성도를 떨어뜨릴 필요가 있다.On the other hand, in order to prevent a decrease in luminous intensity at the time of light emission of organic EL, it is necessary to alleviate an excessively acidic state that causes deterioration in lifetime. Since the α-position fluorinated sulfonic acid or bisfluoroalkylsulfonylimide is a super strong acid, proton transfer occurs from the anode layer to which the conductive polymer is applied to the light emitting layer during light emission, thereby lowering the luminous efficiency and lowering the luminous intensity. do. To prevent this, it is necessary to lower the acidity of the dopant polymer.

그래서, 본 발명자들은, 상기의 설폰아마이드기를 갖는 반복 단위를 포함하는 고분자 화합물을, 공액 이중 결합용 폴리머의 도펀트로서 이용한 바, 유기 EL의 고효율과 고수명의 양방을 달성할 수 있는 것이 됨을 발견하여, 본 발명을 완성시켰다.Therefore, the present inventors have found that both high efficiency and long life of organic EL can be achieved by using the above polymer compound containing a repeating unit having a sulfonamide group as a dopant for a polymer for a conjugated double bond. The present invention was completed.

즉, 본 발명은, 도전성 폴리머용 고분자 화합물로서, 하기 화학식(1)로 표시되는 반복 단위 a를 1종 이상 포함하고, 중량 평균 분자량이 1,000∼500,000의 범위인 것인 도전성 폴리머용 고분자 화합물이다.That is, the present invention is a polymer compound for a conductive polymer, comprising at least one repeating unit a represented by the following formula (1), and having a weight average molecular weight in the range of 1,000 to 500,000.

Figure 112018017704619-pat00007
Figure 112018017704619-pat00007

(식 중, R1은 수소 원자 또는 메틸기이고, Rf1은 탄소수 1∼4의 직쇄상, 분기상의 알킬기, 또는 페닐기이며, Rf1 중에 1개 이상의 불소 원자 또는 트라이플루오로메틸기를 갖는다. Z1은 단일 결합, 탄소수 6∼12의 아릴렌기, 또는 -C(=O)-O-R2-이고, R2는 탄소수 1∼12의 직쇄상, 분기상, 환상의 알킬렌기, 탄소수 6∼10의 아릴렌기, 또는 탄소수 2∼10의 알켄일렌기이며, R2 중에 에터기, 카보닐기, 에스터기를 갖고 있어도 된다. a는 0＜a≤1.0이다.)(Wherein, R 1 is a hydrogen atom or a methyl group, Rf 1 is a linear or branched alkyl group having 1 to 4 carbon atoms, or a phenyl group, and has at least one fluorine atom or a trifluoromethyl group in Rf 1 . Z 1 is a single bond, an arylene group having 6 to 12 carbon atoms, or -C(=O)-OR 2 -, and R 2 is a linear, branched, cyclic alkylene group having 1 to 12 carbon atoms, aryl having 6 to 10 carbon atoms It is a lene group or an alkenylene group having 2 to 10 carbon atoms, and may have an ether group, a carbonyl group, or an ester group in R 2 , where a is 0<a≤1.0.)

이하, 본 발명에 대해 상세하게 설명하지만, 본 발명은 이들로 한정되는 것은 아니다.Hereinafter, although this invention is demonstrated in detail, this invention is not limited to these.

한편, 본 발명에 있어서, 「도전성」은 「전기 전도성」을 의미한다.On the other hand, in the present invention, "conductive" means "electrically conductive".

또한, 본 발명에 있어서, a, a1∼a4, b, 및 c는, 각각 반복 단위의 분자내 비율을 나타내고 있다.In the present invention, a, a 1 to a 4 , b, and c each represent an intramolecular ratio of a repeating unit.

본 발명의 도전성 폴리머용 고분자 화합물은, 하기 화학식(1)로 표시되는 반복 단위 a를 포함하는 폴리머이다. 본 발명의 도전성 폴리머용 고분자 화합물은, 화학식(1)로 표시되는 반복 단위 a를 함유함으로써, 특히 투명성이 높은 것이 된다.The polymer compound for conductive polymers of the present invention is a polymer containing a repeating unit a represented by the following general formula (1). The high molecular compound for conductive polymers of this invention becomes a thing with especially high transparency by containing the repeating unit a represented by general formula (1).

Figure 112018017704619-pat00008
Figure 112018017704619-pat00008

(식 중, R1은 수소 원자 또는 메틸기이고, Rf1은 탄소수 1∼4의 직쇄상, 분기상의 알킬기, 또는 페닐기이며, Rf1 중에 1개 이상의 불소 원자 또는 트라이플루오로메틸기를 갖는다. Z1은 단일 결합, 탄소수 6∼12의 아릴렌기, 또는 -C(=O)-O-R2-이고, R2는 탄소수 1∼12의 직쇄상, 분기상, 환상의 알킬렌기, 탄소수 6∼10의 아릴렌기, 또는 탄소수 2∼10의 알켄일렌기이며, R2 중에 에터기, 카보닐기, 에스터기를 갖고 있어도 된다. a는 0＜a≤1.0이다.)(Wherein, R 1 is a hydrogen atom or a methyl group, Rf 1 is a linear or branched alkyl group having 1 to 4 carbon atoms, or a phenyl group, and has at least one fluorine atom or a trifluoromethyl group in Rf 1 . Z 1 is a single bond, an arylene group having 6 to 12 carbon atoms, or -C(=O)-OR 2 -, and R 2 is a linear, branched, cyclic alkylene group having 1 to 12 carbon atoms, aryl having 6 to 10 carbon atoms It is a lene group or an alkenylene group having 2 to 10 carbon atoms, and may have an ether group, a carbonyl group, or an ester group in R 2 , where a is 0<a≤1.0.)

화학식(1) 중, R1은 수소 원자 또는 메틸기이다.In formula (1), R 1 is a hydrogen atom or a methyl group.

Rf1은 탄소수 1∼4의 직쇄상, 분기상의 알킬기, 또는 페닐기이고, Rf1 중에 1개 이상의 불소 원자 또는 트라이플루오로메틸기를 갖는다.Rf 1 is a linear or branched alkyl group or phenyl group having 1 to 4 carbon atoms, and has at least one fluorine atom or a trifluoromethyl group in Rf 1 .

Z1은 단일 결합, 탄소수 6∼12의 아릴렌기, 또는 -C(=O)-O-R2-이고, R2는 탄소수 1∼12의 직쇄상, 분기상, 환상의 알킬렌기, 탄소수 6∼10의 아릴렌기, 또는 탄소수 2∼10의 알켄일렌기이며, R2 중에 에터기, 카보닐기, 에스터기를 갖고 있어도 된다. R2로서 바람직하게는, 메틸렌기, 에틸렌기, 아다만틸렌기, 페닐렌기를 들 수 있다.Z 1 is a single bond, an arylene group having 6 to 12 carbon atoms, or -C(=O)-OR 2 -; R 2 is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms; is an arylene group or an alkenylene group having 2 to 10 carbon atoms, and may have an ether group, a carbonyl group, or an ester group in R 2 . Preferably as R<2> , a methylene group, an ethylene group, an adamantylene group, and a phenylene group are mentioned.

a는 0＜a≤1.0이다.a is 0<a≤1.0.

또한, 상기 화학식(1)로 표시되는 반복 단위 a가, 하기 화학식(3)으로 표시되는 반복 단위 a1∼a4를 포함하는 것인 것이 바람직하다.Further, it is preferable that the repeating unit a represented by the formula (1) includes the repeating units a 1 to a 4 represented by the following formula (3).

Figure 112018017704619-pat00009
Figure 112018017704619-pat00009

(식 중, R1 및 Rf1은 상기와 마찬가지이다. a1, a2, a3, 및 a4는 0≤a1≤1.0, 0≤a2≤1.0, 0≤a3≤1.0, 0≤a4≤1.0, 0＜a1＋a2＋a3＋a4≤1.0이다.)(Wherein, R 1 and Rf 1 are the same as above. a 1 , a 2 , a 3 , and a 4 are 0≤a 1 ≤1.0, 0≤a 2 ≤1.0, 0≤a 3 ≤1.0, 0 ≤a 4 ≤1.0, 0<a 1 +a 2 +a 3 +a 4 ≤1.0)

이와 같은 반복 단위이면, 연료 전지용이나 도전성 재료용의 도펀트로서 더욱 적합한 것이 된다.Such a repeating unit is more suitable as a dopant for fuel cells or conductive materials.

또한, 본 발명의 도전성 폴리머용 고분자 화합물은, 추가로 하기 화학식(2)로 표시되는 반복 단위 b를 갖는 것인 것이 바람직하다. 상기 반복 단위 a가, 폴리스타이렌설폰산의 반복 단위 b와 공중합된 것이면, 도전성이 높은 도펀트 폴리머로서 이용할 수 있다.Moreover, it is preferable that the high molecular compound for conductive polymers of this invention has a repeating unit b further represented by following formula (2). If the repeating unit a is copolymerized with the repeating unit b of polystyrenesulfonic acid, it can be used as a dopant polymer having high conductivity.

Figure 112018017704619-pat00010
Figure 112018017704619-pat00010

(식 중, b는 0＜b＜1.0이다.)(Wherein, b is 0<b<1.0.)

또한, 후술과 같이, 본 발명의 도전성 폴리머용 고분자 화합물은, 반복 단위 a, 반복 단위 b 이외의 반복 단위 c를 갖고 있어도 된다.Moreover, as mentioned later, the high molecular compound for conductive polymers of this invention may have repeating unit c other than the repeating unit a and the repeating unit b.

또한, 본 발명의 도전성 폴리머용 고분자 화합물은, 중량 평균 분자량이 1,000∼500,000, 바람직하게는 2,000∼200,000의 범위인 것이다. 중량 평균 분자량이 1,000 미만이면, 내열성이 뒤떨어지는 것이 된다. 한편, 중량 평균 분자량이 500,000을 초과하면, 점도가 상승하여, 작업성이 악화되고, 유기 용제나 물로의 용해성이 저하된다.Moreover, the high molecular weight compound for conductive polymers of this invention is 1,000-500,000, Preferably it is the range of 2,000-200,000. When the weight average molecular weight is less than 1,000, it is inferior in heat resistance. On the other hand, when a weight average molecular weight exceeds 500,000, a viscosity will rise, workability|operativity will deteriorate, and the solubility to an organic solvent and water will fall.

한편, 중량 평균 분자량(Mw)은, 용제로서 물, 다이메틸폼아마이드(DMF), 테트라하이드로퓨란(THF)을 이용한 겔 퍼미에이션 크로마토그래피(GPC)에 의한 폴리스타이렌 환산 측정치이다.In addition, the weight average molecular weight (Mw) is a polystyrene conversion measurement value by gel permeation chromatography (GPC) using water, dimethylformamide (DMF), and tetrahydrofuran (THF) as a solvent.

전술과 같은 본 발명의 도전성 폴리머용 고분자 화합물이면, 유기 용제에 가용이며, 연료 전지용이나 도전성 재료용의 도펀트로서 적합하게 이용되는 특정한 강산의 설폰아마이드기를 갖는 도전성 폴리머용 고분자 화합물이 된다.If it is the polymer compound for conductive polymers of the present invention as described above, it is a polymer compound for conductive polymers having a specific strong acid sulfonamide group that is soluble in organic solvents and is suitably used as a dopant for fuel cells or conductive materials.

또한, 본 발명에서는 이와 같은 본 발명의 도전성 폴리머용 고분자 화합물을 제조하는 방법을 제공한다.In addition, the present invention provides a method for producing such a polymer compound for conductive polymers of the present invention.

즉, 본 발명의 제조 방법은, 도전성 폴리머용 고분자 화합물의 제조 방법으로서, That is, the manufacturing method of this invention is a manufacturing method of the high molecular compound for conductive polymers,

카보닐기에 결합한 설폰아마이드기와 리튬, 나트륨, 칼륨, 또는 질소 화합물로 이루어지는 염의 구조를 갖는 모노머를 이용하여 중합 반응을 행하고, 중합 후, 이온 교환에 의해, 상기 카보닐기에 결합한 설폰아마이드기와 리튬, 나트륨, 칼륨, 또는 질소 화합물로 이루어지는 염의 구조를 카보닐기에 결합한 설폰아마이드기로 변환하는 것에 의해, 하기 화학식(1)로 표시되는 반복 단위 a를 포함하는 도전성 폴리머용 고분자 화합물을 제조하는 도전성 폴리머용 고분자 화합물의 제조 방법이다.A polymerization reaction is carried out using a monomer having a salt structure consisting of a sulfonamide group bonded to a carbonyl group and lithium, sodium, potassium, or a nitrogen compound. After polymerization, the sulfonamide group bonded to the carbonyl group is lithium, sodium by ion exchange. Polymeric compound for conductive polymers for producing a polymer compound for a conductive polymer comprising a repeating unit a represented by the following formula (1) by converting the structure of a salt composed of , potassium, or a nitrogen compound to a sulfonamide group bonded to a carbonyl group is a manufacturing method of

Figure 112018017704619-pat00011
Figure 112018017704619-pat00011

(식 중, R1은 수소 원자 또는 메틸기이고, Rf1은 탄소수 1∼4의 직쇄상, 분기상의 알킬기, 또는 페닐기이며, Rf1 중에 1개 이상의 불소 원자 또는 트라이플루오로메틸기를 갖는다. Z1은 단일 결합, 탄소수 6∼12의 아릴렌기, 또는 -C(=O)-O-R2-이고, R2는 탄소수 1∼12의 직쇄상, 분기상, 환상의 알킬렌기, 탄소수 6∼10의 아릴렌기, 또는 탄소수 2∼10의 알켄일렌기이며, R2 중에 에터기, 카보닐기, 에스터기를 갖고 있어도 된다. a는 0＜a≤1.0이다.)(Wherein, R 1 is a hydrogen atom or a methyl group, Rf 1 is a linear or branched alkyl group having 1 to 4 carbon atoms, or a phenyl group, and has at least one fluorine atom or a trifluoromethyl group in Rf 1 . Z 1 is a single bond, an arylene group having 6 to 12 carbon atoms, or -C(=O)-OR 2 -, and R 2 is a linear, branched, cyclic alkylene group having 1 to 12 carbon atoms, aryl having 6 to 10 carbon atoms It is a lene group or an alkenylene group having 2 to 10 carbon atoms, and may have an ether group, a carbonyl group, or an ester group in R 2 , where a is 0<a≤1.0.)

여기에서, 상기 카보닐기에 결합한 설폰아마이드기와 리튬, 나트륨, 칼륨, 또는 질소 화합물로 이루어지는 염의 구조를 갖는 모노머를 이용하여 중합 반응을 행하여 얻어진 중합체는, 하기 화학식(4)로 표시되는 반복 단위를 포함하는 것인 것이 바람직하다.Here, the polymer obtained by performing a polymerization reaction using a monomer having a salt structure consisting of a sulfonamide group bonded to a carbonyl group and lithium, sodium, potassium, or a nitrogen compound includes a repeating unit represented by the following formula (4) It is preferable to do

Figure 112018017704619-pat00012
Figure 112018017704619-pat00012

(식 중, R1, Z1, Rf1, 및 a는 상기와 마찬가지이고, X는 리튬, 나트륨, 칼륨, 또는 하기 화학식(5)로 표시되는 질소 화합물이다.)(Wherein, R 1 , Z 1 , Rf 1 , and a are the same as above, and X is lithium, sodium, potassium, or a nitrogen compound represented by the following formula (5).)

Figure 112018017704619-pat00013
Figure 112018017704619-pat00013

(식 중, R101d, R101e, R101f, 및 R101g는, 각각 수소 원자, 혹은 탄소수 1∼12의 직쇄상, 분기상 또는 환상의 알킬기, 알켄일기, 옥소알킬기 또는 옥소알켄일기, 탄소수 6∼20의 아릴기, 또는 탄소수 7∼12의 아르알킬기 또는 아릴옥소알킬기를 나타내고, 이들 기의 수소 원자의 일부 또는 전부가 알콕시기에 의해 치환되어 있어도 된다. R101d와 R101e, R101d와 R101e와 R101f는 환을 형성해도 되고, 환을 형성하는 경우에는, R101d와 R101e 및 R101d와 R101e와 R101f는 탄소수 3∼10의 알킬렌기, 또는 식 중의 질소 원자를 환 중에 갖는 헤테로방향족환을 나타낸다.)(Wherein, R 101d , R 101e , R 101f , and R 101g are each a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, and 6 carbon atoms represents an aryl group of -20, an aralkyl group of 7 to 12 carbon atoms, or an aryloxoalkyl group, and some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group.R 101d and R 101e , R 101d and R 101e and R 101f may form a ring, and in the case of forming a ring, R 101d and R 101e and R 101d and R 101e and R 101f are an alkylene group having 3 to 10 carbon atoms, or a heterocyclic group having a nitrogen atom in the ring. represents an aromatic ring.)

이와 같은 반복 단위이면, 이온 교환에 의해 용이하게 상기 화학식(1)로 표시되는 반복 단위 a로 변환되기 때문에 바람직하다.Such a repeating unit is preferable because it is easily converted into the repeating unit a represented by the formula (1) by ion exchange.

본 발명의 제조 방법에서 이용되는 설폰아마이드기와 리튬, 나트륨, 칼륨, 또는 질소 화합물로 이루어지는 염의 구조를 갖고, 상기 화학식(1)로 표시되는 반복 단위 a를 얻기 위한 모노머로서는, 구체적으로는 하기의 것을 예시할 수 있다.As a monomer for obtaining the repeating unit a, which has a salt structure of a sulfonamide group and a lithium, sodium, potassium, or nitrogen compound used in the production method of the present invention, and is represented by the above formula (1), specifically, the following are can be exemplified.

Figure 112018017704619-pat00014
Figure 112018017704619-pat00014

Figure 112018017704619-pat00015
Figure 112018017704619-pat00015

Figure 112018017704619-pat00016
Figure 112018017704619-pat00016

(식 중, R1은 상기와 마찬가지이고, X는 리튬, 나트륨, 칼륨, 또는 질소 화합물이다.)(Wherein, R 1 is the same as above, and X is lithium, sodium, potassium, or a nitrogen compound.)

또한, 전술한 바와 같이 화학식(1)로 표시되는 반복 단위 a로서는, 전술한 화학식(3)으로 표시되는 반복 단위 a1∼a4를 포함하는 것이 바람직하다.As described above, the repeating unit a represented by the formula (1) preferably includes the repeating units a 1 to a 4 represented by the formula (3) described above.

또한, 전술한 바와 같이, 본 발명의 도전성 폴리머용 고분자 화합물로서는, 화학식(2)로 표시되는 반복 단위 b를 갖는 것이 바람직하고, 이와 같은 반복 단위 b를 얻기 위한 모노머로서는, 구체적으로는 하기의 것을 예시할 수 있다.As described above, the polymer compound for a conductive polymer of the present invention preferably has a repeating unit b represented by the formula (2). As a monomer for obtaining such a repeating unit b, specifically, the following are can be exemplified.

Figure 112018017704619-pat00017
Figure 112018017704619-pat00017

(식 중, X2는 수소 원자, 리튬, 나트륨, 칼륨, 질소 화합물, 또는 설포늄 화합물이다.)(Wherein, X 2 is a hydrogen atom, lithium, sodium, potassium, a nitrogen compound, or a sulfonium compound.)

상기 X2가 질소 화합물인 경우의 예로서는, 하기 화학식(5)로 표시되는 화합물을 들 수 있다.Examples of the case where X 2 is a nitrogen compound include compounds represented by the following general formula (5).

Figure 112018017704619-pat00018
Figure 112018017704619-pat00018

(식 중, R101d, R101e, R101f, 및 R101g는, 각각 수소 원자, 혹은 탄소수 1∼12의 직쇄상, 분기상 또는 환상의 알킬기, 알켄일기, 옥소알킬기 또는 옥소알켄일기, 탄소수 6∼20의 아릴기, 또는 탄소수 7∼12의 아르알킬기 또는 아릴옥소알킬기를 나타내고, 이들 기의 수소 원자의 일부 또는 전부가 알콕시기에 의해 치환되어 있어도 된다. R101d와 R101e, R101d와 R101e와 R101f는 환을 형성해도 되고, 환을 형성하는 경우에는, R101d와 R101e 및 R101d와 R101e와 R101f는 탄소수 3∼10의 알킬렌기, 또는 식 중의 질소 원자를 환 중에 갖는 헤테로방향족환을 나타낸다.)(Wherein, R 101d , R 101e , R 101f , and R 101g are each a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, and 6 carbon atoms represents an aryl group of -20, an aralkyl group of 7 to 12 carbon atoms, or an aryloxoalkyl group, and some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group.R 101d and R 101e , R 101d and R 101e and R 101f may form a ring, and in the case of forming a ring, R 101d and R 101e and R 101d and R 101e and R 101f are an alkylene group having 3 to 10 carbon atoms, or a heterocyclic group having a nitrogen atom in the ring. represents an aromatic ring.)

또한, 전술한 바와 같이, 본 발명의 도전성 폴리머용 고분자 화합물은, 반복 단위 a, 반복 단위 b 이외의 반복 단위 c를 갖고 있어도 되고, 이 반복 단위 c를 얻기 위한 모노머로서는, (메트)아크릴계, 스타이렌계, 바이닐나프탈렌계, 바이닐실레인계, 아세나프틸렌, 인덴, 바이닐카바졸 등 외에, 규소 원자나 불소 원자를 갖는 모노머를 들 수 있다.In addition, as described above, the polymer compound for conductive polymers of the present invention may have a repeating unit c other than the repeating unit a and the repeating unit b, and as a monomer for obtaining the repeating unit c, a (meth)acrylic-based, styl The monomer which has a silicon atom and a fluorine atom other than ene type|system|group, vinyl naphthalene type, vinylsilane type, acenaphthylene, indene, vinyl carbazole, etc. is mentioned.

반복 단위 c를 얻기 위한 모노머로서는, 구체적으로는 하기의 것을 예시할 수 있다.As a monomer for obtaining the repeating unit c, the following can be illustrated specifically.

Figure 112018017704619-pat00019
Figure 112018017704619-pat00019

Figure 112018017704619-pat00020
Figure 112018017704619-pat00020

Figure 112018017704619-pat00021
Figure 112018017704619-pat00021

Figure 112018017704619-pat00022
Figure 112018017704619-pat00022

Figure 112018017704619-pat00023
Figure 112018017704619-pat00023

Figure 112018017704619-pat00024
Figure 112018017704619-pat00024

Figure 112018017704619-pat00025
Figure 112018017704619-pat00025

본 발명의 도전성 폴리머용 고분자 화합물을 합성하는 방법으로서는, 예를 들어 전술한 모노머 중 원하는 모노머를, 용제 중, 라디칼 중합 개시제를 가하고 가열 중합을 행함으로써, 공중합체의 고분자 화합물을 얻는 방법을 들 수 있다.As a method of synthesizing the polymer compound for a conductive polymer of the present invention, for example, a method of obtaining a polymer compound of a copolymer by adding a radical polymerization initiator to a desired monomer among the above-mentioned monomers in a solvent and performing heating polymerization. have.

중합 시에 사용하는 용제로서는, 물, 메탄올, 에탄올, n-프로판올, 아이소프로필알코올, 메톡시에탄올, 에톡시에탄올, n-뷰탄올, 에틸렌 글라이콜, 프로필렌 글라이콜, 글리세린, 다이에틸렌 글라이콜, 다이메틸설포아마이드, 다이메틸아세트아마이드, 아세톤, 다이메틸설폭사이드, N-메틸피롤리돈, 톨루엔, 벤젠, 테트라하이드로퓨란, 다이에틸 에터, 다이옥세인, 사이클로헥세인, 사이클로펜테인, 메틸 에틸 케톤, γ-뷰티로락톤 등을 예시할 수 있다.As a solvent used during polymerization, water, methanol, ethanol, n-propanol, isopropyl alcohol, methoxyethanol, ethoxyethanol, n-butanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol Lycol, dimethyl sulfoamide, dimethylacetamide, acetone, dimethyl sulfoxide, N-methylpyrrolidone, toluene, benzene, tetrahydrofuran, diethyl ether, dioxane, cyclohexane, cyclopentane, methyl ethyl ketone, γ-butyrolactone, and the like can be exemplified.

라디칼 중합 개시제로서는, 다이-t-뷰틸퍼옥사이드, 다이큐밀퍼옥사이드, t-뷰틸큐밀퍼옥사이드, 벤조일퍼옥사이드, 다이라우릴퍼옥사이드, 큐멘하이드로퍼옥사이드, t-뷰틸하이드로퍼옥사이드, t-뷰틸퍼옥시아이소뷰티레이트, 과황산 칼륨, 과황산 암모늄, 과산화수소수, 2,2'-아조비스아이소뷰티로나이트릴(AIBN), 2,2'-아조비스(2,4-다이메틸발레로나이트릴), 다이메틸 2,2-아조비스(2-메틸프로피오네이트), 라우로일퍼옥사이드, 2,2'-아조비스(2-아미디노프로페인)이염산염, 또는 4,4'-아조비스(4-사이아노발레르산)의 알칼리 금속염 또는 암모늄염 등을 예시할 수 있다.Examples of the radical polymerization initiator include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butyl Tylperoxyisobutyrate, potassium persulfate, ammonium persulfate, aqueous hydrogen peroxide, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis (2,4-dimethylvaleronitrile) Lil), dimethyl 2,2-azobis(2-methylpropionate), lauroyl peroxide, 2,2'-azobis(2-amidinopropane)dihydrochloride, or 4,4'-azo An alkali metal salt or an ammonium salt of bis(4-cyanovaleric acid), etc. can be illustrated.

반응 온도는, 바람직하게는 50∼80℃이고, 반응 시간은 바람직하게는 2∼100시간, 보다 바람직하게는 5∼20시간이다.The reaction temperature is preferably 50 to 80°C, and the reaction time is preferably 2 to 100 hours, more preferably 5 to 20 hours.

본 발명의 도전성 폴리머용 고분자 화합물에 있어서, 화학식(1)로 표시되는 반복 단위 a가 되는 모노머는 1종류여도 2종류 이상의 조합이어도 되지만, 중합성을 높이는 데에는 메타크릴 타입과 스타이렌 타입의 모노머를 조합하는 것이 바람직하다.In the polymer compound for conductive polymers of the present invention, one type or a combination of two or more types may be used as the monomer to be the repeating unit a represented by the formula (1). It is preferable to combine them.

또한, 반복 단위 a를 형성하는 2종류 이상의 모노머가 랜덤으로 공중합되어 있어도, 각각이 블록으로 공중합되어 있어도 된다. 블록 공중합 폴리머(블록 코폴리머)를 도전막으로 했을 경우는, 2종류 이상의 반복 단위 a로 이루어지는 반복 단위 부분끼리가 응집하여 해도(海島) 구조를 형성하는 것에 의해 도전성이 향상되는 이점이 기대된다.Moreover, even if two or more types of monomers which form the repeating unit a are copolymerized at random, each may be copolymerized by a block. When a block copolymer (block copolymer) is used as a conductive film, the advantage of improving conductivity is expected by the aggregation of repeating unit portions composed of two or more kinds of repeating units a to form a sea-island structure.

또한, 반복 단위 a∼c를 얻기 위한 모노머가 랜덤으로 공중합되어 있어도, 각각이 블록으로 공중합되어 있어도 된다. 이 경우도, 전술한 반복 단위 a의 경우와 마찬가지로, 블록 코폴리머로 함으로써 도전율이 향상되는 이점이 기대된다.In addition, the monomers for obtaining the repeating units a to c may be copolymerized at random, or each may be copolymerized by a block. Also in this case, similarly to the case of the above-described repeating unit a, an advantage in that the conductivity is improved by using the block copolymer is expected.

라디칼 중합으로 랜덤 공중합을 행하는 경우는, 공중합을 행하는 모노머나 라디칼 중합 개시제를 혼합하고 가열에 의해 중합을 행하는 방법이 일반적이다. 제 1 모노머와 라디칼 중합 개시제 존재 하에서 중합을 개시하고, 후에 제 2 모노머를 첨가했을 경우는, 폴리머 분자의 편측이 제 1 모노머가 중합한 구조이고, 다른 편측이 제 2 모노머가 중합한 구조가 된다. 그렇지만 이 경우, 중간 부분에는 제 1과 제 2 모노머의 반복 단위가 혼재하고 있어, 블록 코폴리머와는 형태가 상이하다. 라디칼 중합으로 블록 코폴리머를 형성하는 데에는, 리빙 라디칼 중합이 바람직하게 이용된다.When performing random copolymerization by radical polymerization, the method of mixing the monomer which copolymerizes and a radical polymerization initiator, and superposing|polymerizing by heating is common. When polymerization is started in the presence of a first monomer and a radical polymerization initiator, and a second monomer is added thereafter, one side of the polymer molecule is a structure in which the first monomer is polymerized, and the other side is a structure in which the second monomer is polymerized. . However, in this case, repeating units of the first and second monomers are mixed in the middle portion, and thus the form is different from that of the block copolymer. In order to form a block copolymer by radical polymerization, living radical polymerization is used preferably.

RAFT 중합(Reversible Addition Fragmentation chain Transfer polymerization)으로 불리는 리빙 라디칼의 중합 방법은, 폴리머 말단의 라디칼이 항상 살아 있으므로, 제 1 모노머로 중합을 개시하고, 이들이 소비된 단계에서 제 2 모노머를 첨가하는 것에 의해 제 1과 제 2 반복 단위에 의한 블록 코폴리머를 형성하는 것이 가능하다. 또한, 제 1 모노머로 중합을 개시하고, 이것이 소비된 시점에서 제 2 모노머를 첨가하고, 그 다음에 제 3 모노머를 첨가했을 경우는 트라이블록 코폴리머를 형성할 수도 있다.The polymerization method of living radicals, called RAFT polymerization (Reversible Addition Fragmentation chain transfer polymerization), is because the radicals at the ends of the polymer are always alive, so by initiating polymerization with the first monomer and adding the second monomer at the stage where they are consumed It is possible to form block copolymers with first and second repeating units. It is also possible to form a triblock copolymer by initiating polymerization with the first monomer, adding the second monomer when it is consumed, and then adding the third monomer.

RAFT 중합을 행한 경우는 분자량 분포(분산도)가 좁은 협(狹)분산 폴리머가 형성되는 특징이 있고, 특히 모노머를 한 번에 첨가하여 RAFT 중합을 행한 경우는, 보다 분자량 분포가 좁은 폴리머를 형성할 수 있다.When RAFT polymerization is performed, a narrowly dispersed polymer with a narrow molecular weight distribution (dispersity) is formed. In particular, when RAFT polymerization is performed by adding a monomer at a time, a polymer with a narrower molecular weight distribution is formed can do.

한편, 본 발명의 도전성 폴리머용 고분자 화합물에 있어서는, 분자량 분포(Mw/Mn)는 1.0∼2.0인 것이 바람직하고, 특히 1.0∼1.5로 협분산인 것이 바람직하다. 협분산이면, 고분자 화합물을 이용하여 합성한 도전성 폴리머의 도전율이 불균일해지는 것을 막을 수 있다.On the other hand, in the polymer compound for conductive polymers of the present invention, the molecular weight distribution (Mw/Mn) is preferably from 1.0 to 2.0, and particularly preferably from 1.0 to 1.5 and narrowly dispersed. If it is narrow dispersion, it can prevent that the electrical conductivity of the electrically conductive polymer synthesize|combined using a high molecular compound becomes non-uniform|heterogenous.

RAFT 중합을 행하려면 연쇄 이동제가 필요하고, 구체적으로는 2-사이아노-2-프로필벤조싸이오에이트, 4-사이아노-4-페닐카보노싸이오일싸이오펜탄산, 2-사이아노-2-프로필도데실트라이싸이오카보네이트, 4-사이아노-4-[(도데실설파닐싸이오카보닐)설판일]펜탄산, 2-(도데실싸이오카보노싸이오일싸이오)-2-메틸프로판산, 사이아노메틸도데실싸이오카보네이트, 사이아노메틸메틸(페닐)카바모싸이오에이트, 비스(싸이오벤조일)다이설파이드, 비스(도데실설파닐싸이오카보닐)다이설파이드를 들 수 있다. 이들 중에서는, 특히 2-사이아노-2-프로필벤조싸이오에이트가 바람직하다.RAFT polymerization requires a chain transfer agent, specifically 2-cyano-2-propylbenzothioate, 4-cyano-4-phenylcarbonothioylthiopentanoic acid, 2-cyano-2- Propyldodecyltrithiocarbonate, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, 2-(dodecylthiocarbonothioylthio)-2-methylpropanoic acid , cyanomethyldodecylthiocarbonate, cyanomethylmethyl(phenyl)carbamothioate, bis(thiobenzoyl)disulfide, and bis(dodecylsulfanylthiocarbonyl)disulfide. Among these, 2-cyano-2-propylbenzothioate is particularly preferable.

여기에서, 반복 단위 a∼c의 비율은, 0＜a≤1.0, 0≤b＜1.0, 0≤c＜1.0이고, 바람직하게는 0.1≤a≤0.9, 0.1≤b≤0.9, 0≤c≤0.8이며, 보다 바람직하게는 0.2≤a≤0.8, 0.2≤b≤0.8, 0≤c≤0.5이다.Here, the ratio of repeating units a to c is 0<a≤1.0, 0≤b<1.0, 0≤c<1.0, preferably 0.1≤a≤0.9, 0.1≤b≤0.9, 0≤c≤ 0.8, and more preferably 0.2 ≤ a ≤ 0.8, 0.2 ≤ b ≤ 0.8, and 0 ≤ c ≤ 0.5.

한편, a＋b＋c=1인 것이 바람직하다.On the other hand, it is preferable that a+b+c=1.

본 발명의 도전성 폴리머용 고분자 화합물의 제조 방법에서는, 전술한 바와 같이 하여 모노머를 중합시킨 후, 이온 교환에 의해, 카보닐기에 결합한 설폰아마이드기와 리튬, 나트륨, 칼륨, 또는 질소 화합물로 이루어지는 염의 구조를 카보닐기에 결합한 설폰아마이드기로 변환한다.In the method for producing the polymer compound for a conductive polymer of the present invention, after polymerization of the monomer as described above, the structure of a salt composed of a sulfonamide group bonded to a carbonyl group and lithium, sodium, potassium, or a nitrogen compound is obtained by ion exchange. Converts to a sulfonamide group bonded to a carbonyl group.

이 때, 이온 교환은, 예를 들어 이온 교환 수지를 이용하여 행하면 된다.At this time, ion exchange may be performed using, for example, an ion exchange resin.

전술과 같은 방법으로, 상기 화학식(1)로 표시되는 반복 단위 a를 포함하는 도전성 폴리머용 고분자 화합물을 용이하게 제조할 수 있다.In the same manner as described above, a polymer compound for a conductive polymer including the repeating unit a represented by the formula (1) can be easily prepared.

이상과 같이, 본 발명의 도전성 폴리머용 고분자 화합물이면, 유기 용제에 가용이며, 연료 전지용이나 도전성 재료용의 도펀트로서 적합하게 이용되는 특정한 초강산의 설폰아마이드기를 갖는 도전성 폴리머용 고분자 화합물이 된다.As described above, if the polymer compound for conductive polymers of the present invention is soluble in organic solvents, it becomes a polymer compound for conductive polymers having a sulfonamide group of a specific super-strong acid that is suitably used as a dopant for fuel cells or conductive materials.

이 도전성 폴리머용 고분자 화합물을 연료 전지에 이용하는 것에 의해, 고유전율인 연료 전지용 재료를 형성할 수 있다. 또한, 공액 이중 결합 폴리머용의 도펀트로서 이용하는 것에 의해, 고투명, 고도전성이고 내구성이 높은 도전막을 형성하는 것이 가능해진다. 본 발명의 도전성 폴리머용 고분자 화합물은 특정한 초강산의 설폰아마이드기를 갖고 있기 때문에, 강한 이온 결합에 의해 도펀트로서의 능력이 높고, 또한 이온으로서의 안정성이 높은 것이 된다. 그 때문에, 이것을 도전성 재료로서 이용했을 경우에 높은 도전성과 안정성을 나타낸다. 더욱이, 유기 용제로의 용해성이 우수하기 때문에, 유기 EL 조명용의 도전막에 이용함으로써, 유기 EL 소자의 열화를 방지할 수 있다.By using this polymer compound for conductive polymers in a fuel cell, a fuel cell material having a high dielectric constant can be formed. Moreover, by using it as a dopant for conjugated double bond polymers, it becomes possible to form a highly transparent, highly conductive, and durable electrically conductive film. Since the high molecular compound for conductive polymers of the present invention has a sulfonamide group of a specific super acid, its ability as a dopant is high due to its strong ionic bond, and its stability as an ion is high. Therefore, when this is used as an electroconductive material, high electroconductivity and stability are shown. Moreover, since it is excellent in solubility to an organic solvent, deterioration of organic electroluminescent element can be prevented by using for the electrically conductive film for organic electroluminescent.

또한, 본 발명의 제조 방법이면, 이와 같은 본 발명의 도전성 폴리머용 고분자 화합물을 용이하게 제조할 수 있다.Moreover, if it is the manufacturing method of this invention, such a high molecular compound for conductive polymers of this invention can be manufactured easily.

실시예Example

이하, 실시예를 이용하여 본 발명을 구체적으로 설명하지만, 본 발명은 이들로 한정되는 것은 아니다.Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited thereto.

이하에 실시예의 합성에서 이용한 모노머를 나타낸다.The monomers used in the synthesis|combination of an Example are shown below.

Figure 112018017704619-pat00026
Figure 112018017704619-pat00026

[실시예 1][Example 1]

질소 분위기하, 64℃에서 교반한 메탄올 37.5g에, 모노머 1의 36.4g과 2,2'-아조비스(아이소뷰티르산) 다이메틸 5.13g을 메탄올 112.5g에 녹인 용액을 4시간에 걸쳐 적하했다. 추가로 64℃에서 4시간 교반했다. 실온까지 냉각한 후, 1,000g의 아세트산 에틸에 격렬하게 교반하면서 적하했다. 생성된 고형물을 여과하여 취하고, 50℃에서 15시간 진공 건조하여, 백색 중합체 23.0g을 얻었다.A solution of 36.4 g of monomer 1 and 5.13 g of 2,2'-azobis(isobutyric acid) dimethyl in 112.5 g of methanol was added dropwise to 37.5 g of methanol stirred at 64°C in a nitrogen atmosphere over 4 hours. . Furthermore, it stirred at 64 degreeC for 4 hours. After cooling to room temperature, it was dripped at 1,000 g of ethyl acetate, stirring vigorously. The resulting solid was collected by filtration and vacuum dried at 50° C. for 15 hours to obtain 23.0 g of a white polymer.

얻어진 백색 중합체를 순수 912g에 용해하고, 이온 교환 수지를 이용하여 벤질트라이메틸암모늄염을 설폰아마이드기로 변환했다. 얻어진 중합체를 19F-NMR, 1H-NMR, 및 GPC 측정한 바, 이하의 분석 결과가 되었다.The obtained white polymer was dissolved in 912 g of pure water, and the benzyl trimethylammonium salt was converted into a sulfonamide group using an ion exchange resin. When the obtained polymer was measured by 19 F-NMR, 1 H-NMR, and GPC, the following analysis results were obtained.

중량 평균 분자량(Mw)=35,000Weight average molecular weight (Mw) = 35,000

분자량 분포(Mw/Mn)=1.69Molecular weight distribution (Mw/Mn) = 1.69

이 고분자 화합물을 (폴리머 1)로 한다.Let this high molecular compound be (Polymer 1).

Figure 112018017704619-pat00027
Figure 112018017704619-pat00027

[실시예 2][Example 2]

질소 분위기하, 64℃에서 교반한 메탄올 37.5g에, 모노머 1의 20.9g과 스타이렌설폰산 리튬 9.5g과 2,2'-아조비스(아이소뷰티르산) 다이메틸 5.13g을 메탄올 112.5g에 녹인 용액을 4시간에 걸쳐 적하했다. 추가로 64℃에서 4시간 교반했다. 실온까지 냉각한 후, 1,000g의 아세트산 에틸에 격렬하게 교반하면서 적하했다. 생성된 고형물을 여과하여 취하고, 50℃에서 15시간 진공 건조하여 백색 중합체 29.3g을 얻었다.A solution of 20.9 g of Monomer 1, 9.5 g of lithium styrenesulfonate, and 5.13 g of 2,2'-azobis(isobutyric acid) dimethyl dissolved in 112.5 g of methanol in 37.5 g of methanol stirred at 64°C under a nitrogen atmosphere. was added dropwise over 4 hours. Furthermore, it stirred at 64 degreeC for 4 hours. After cooling to room temperature, it was dripped at 1,000 g of ethyl acetate, stirring vigorously. The resulting solid was collected by filtration and vacuum dried at 50° C. for 15 hours to obtain 29.3 g of a white polymer.

얻어진 백색 중합체를 순수 912g에 용해하고, 이온 교환 수지를 이용하여 벤질트라이메틸암모늄염과 리튬염을 설폰아마이드기와 설포기로 각각 변환했다. 얻어진 중합체를 19F-NMR, 1H-NMR, 및 GPC 측정한 바, 이하의 분석 결과가 되었다.The obtained white polymer was dissolved in 912 g of pure water, and the benzyl trimethylammonium salt and the lithium salt were respectively converted into a sulfonamide group and a sulfo group using an ion exchange resin. When the obtained polymer was measured by 19 F-NMR, 1 H-NMR, and GPC, the following analysis results were obtained.

공중합 조성비(몰비) 모노머 1:스타이렌설폰산=0.5:0.5Copolymerization composition ratio (molar ratio) Monomer 1: Styrenesulfonic acid = 0.5: 0.5

중량 평균 분자량(Mw)=41,000Weight average molecular weight (Mw) = 41,000

분자량 분포(Mw/Mn)=1.93Molecular weight distribution (Mw/Mn)=1.93

이 고분자 화합물을 (폴리머 2)로 한다.Let this high molecular compound be (Polymer 2).

Figure 112018017704619-pat00028
Figure 112018017704619-pat00028

[실시예 3][Example 3]

질소 분위기하, 64℃에서 교반한 메탄올 37.5g에, 모노머 2의 41.7g과 2,2'-아조비스(아이소뷰티르산) 다이메틸 5.13g을 메탄올 112.5g에 녹인 용액을 4시간에 걸쳐 적하했다. 추가로 64℃에서 4시간 교반했다. 실온까지 냉각한 후, 1,000g의 아세트산 에틸에 격렬하게 교반하면서 적하했다. 생성된 고형물을 여과하여 취하고, 50℃에서 15시간 진공 건조하여, 백색 중합체 33.2g을 얻었다.A solution of 41.7 g of monomer 2 and 5.13 g of 2,2'-azobis(isobutyric acid) dimethyl in 112.5 g of methanol was added dropwise to 37.5 g of methanol stirred at 64°C in a nitrogen atmosphere over 4 hours. . Furthermore, it stirred at 64 degreeC for 4 hours. After cooling to room temperature, it was dripped at 1,000 g of ethyl acetate, stirring vigorously. The resulting solid was collected by filtration and vacuum dried at 50° C. for 15 hours to obtain 33.2 g of a white polymer.

얻어진 백색 중합체를 순수 912g에 용해하고, 이온 교환 수지를 이용하여 나트륨염을 설폰아마이드기로 변환했다. 얻어진 중합체를 19F-NMR, 1H-NMR, 및 GPC 측정한 바, 이하의 분석 결과가 되었다.The obtained white polymer was dissolved in 912 g of pure water, and the sodium salt was converted into a sulfonamide group using an ion exchange resin. When the obtained polymer was measured by 19 F-NMR, 1 H-NMR, and GPC, the following analysis results were obtained.

중량 평균 분자량(Mw)=49,000Weight average molecular weight (Mw) = 49,000

분자량 분포(Mw/Mn)=1.51Molecular weight distribution (Mw/Mn)=1.51

이 고분자 화합물을 (폴리머 3)으로 한다.Let this high molecular compound be (Polymer 3).

Figure 112018017704619-pat00029
Figure 112018017704619-pat00029

[실시예 4][Example 4]

질소 분위기하, 64℃에서 교반한 메탄올 37.5g에, 모노머 3의 17.2g과 스타이렌설폰산 리튬 9.5g과 2,2'-아조비스(아이소뷰티르산) 다이메틸 5.13g을 메탄올 112.5g에 녹인 용액을 4시간에 걸쳐 적하했다. 추가로 64℃에서 4시간 교반했다. 실온까지 냉각한 후, 1,000g의 아세트산 에틸에 격렬하게 교반하면서 적하했다. 생성된 고형물을 여과하여 취하고, 50℃에서 15시간 진공 건조하여 백색 중합체 24.1g을 얻었다.A solution of 17.2 g of Monomer 3, 9.5 g of lithium styrenesulfonate, and 5.13 g of 2,2'-azobis(isobutyric acid) dimethyl dissolved in 112.5 g of methanol in 37.5 g of methanol stirred at 64°C under a nitrogen atmosphere. was added dropwise over 4 hours. Furthermore, it stirred at 64 degreeC for 4 hours. After cooling to room temperature, it was dripped at 1,000 g of ethyl acetate, stirring vigorously. The resulting solid was collected by filtration and vacuum dried at 50° C. for 15 hours to obtain 24.1 g of a white polymer.

얻어진 백색 중합체를 순수 912g에 용해하고, 이온 교환 수지를 이용하여 리튬염을 설폰아마이드기와 설포기로 각각 변환했다. 얻어진 중합체를 19F-NMR, 1H-NMR, 및 GPC 측정한 바, 이하의 분석 결과가 되었다.The obtained white polymer was dissolved in 912 g of pure water, and the lithium salt was converted into a sulfonamide group and a sulfo group using an ion exchange resin, respectively. When the obtained polymer was measured by 19 F-NMR, 1 H-NMR, and GPC, the following analysis results were obtained.

공중합 조성비(몰비) 모노머 3:스타이렌설폰산=0.5:0.5Copolymerization composition ratio (molar ratio) monomer 3: styrene sulfonic acid = 0.5: 0.5

중량 평균 분자량(Mw)=41,000Weight average molecular weight (Mw) = 41,000

분자량 분포(Mw/Mn)=1.63Molecular weight distribution (Mw/Mn)=1.63

이 고분자 화합물을 (폴리머 4)로 한다.Let this high molecular compound be (Polymer 4).

Figure 112018017704619-pat00030
Figure 112018017704619-pat00030

[실시예 5][Example 5]

질소 분위기하, 64℃에서 교반한 메탄올 37.5g에, 모노머 4의 30.1g과 2,2'-아조비스(아이소뷰티르산) 다이메틸 5.13g을 메탄올 112.5g에 녹인 용액을 4시간에 걸쳐 적하했다. 추가로 64℃에서 4시간 교반했다. 실온까지 냉각한 후, 1,000g의 아세트산 에틸에 격렬하게 교반하면서 적하했다. 생성된 고형물을 여과하여 취하고, 50℃에서 15시간 진공 건조하여, 백색 중합체 27.5g을 얻었다.A solution of 30.1 g of monomer 4 and 5.13 g of 2,2'-azobis(isobutyric acid) dimethyl in 112.5 g of methanol was added dropwise to 37.5 g of methanol stirred at 64°C in a nitrogen atmosphere over 4 hours. . Furthermore, it stirred at 64 degreeC for 4 hours. After cooling to room temperature, it was dripped at 1,000 g of ethyl acetate, stirring vigorously. The resulting solid was collected by filtration and vacuum dried at 50°C for 15 hours to obtain 27.5 g of a white polymer.

얻어진 백색 중합체를 순수 912g에 용해하고, 이온 교환 수지를 이용하여 나트륨염을 설폰아마이드기로 변환했다. 얻어진 중합체를 19F-NMR, 1H-NMR, 및 GPC 측정한 바, 이하의 분석 결과가 되었다.The obtained white polymer was dissolved in 912 g of pure water, and the sodium salt was converted into a sulfonamide group using an ion exchange resin. When the obtained polymer was measured by 19 F-NMR, 1 H-NMR, and GPC, the following analysis results were obtained.

중량 평균 분자량(Mw)=38,000Weight average molecular weight (Mw) = 38,000

분자량 분포(Mw/Mn)=1.49Molecular weight distribution (Mw/Mn)=1.49

이 고분자 화합물을 (폴리머 5)로 한다.Let this high molecular compound be (Polymer 5).

Figure 112018017704619-pat00031
Figure 112018017704619-pat00031

[실시예 6][Example 6]

질소 분위기하, 64℃에서 교반한 메탄올 37.5g에, 모노머 1의 29.1g, 메타크릴산 3,5-비스(헥사플루오로-2-하이드록시-2-프로필)사이클로헥실 10g과 2,2'-아조비스(아이소뷰티르산) 다이메틸 5.13g을 메탄올 112.5g에 녹인 용액을 4시간에 걸쳐 적하했다. 추가로 64℃에서 4시간 교반했다. 실온까지 냉각한 후, 1,000g의 아세트산 에틸에 격렬하게 교반하면서 적하했다. 생성된 고형물을 여과하여 취하고, 50℃에서 15시간 진공 건조하여, 백색 중합체 37.5g을 얻었다.In 37.5 g of methanol stirred at 64°C in a nitrogen atmosphere, 29.1 g of monomer 1, 3,5-bis(hexafluoro-2-hydroxy-2-propyl) cyclohexyl methacrylic acid 10g and 2,2' - A solution of 5.13 g of azobis(isobutyric acid) dimethyl dissolved in 112.5 g of methanol was added dropwise over 4 hours. Furthermore, it stirred at 64 degreeC for 4 hours. After cooling to room temperature, it was dripped at 1,000 g of ethyl acetate, stirring vigorously. The resulting solid was collected by filtration and vacuum dried at 50°C for 15 hours to obtain 37.5 g of a white polymer.

얻어진 백색 중합체를 순수 912g에 용해하고, 이온 교환 수지를 이용하여 벤질트라이메틸암모늄염을 설폰아마이드기로 변환했다. 얻어진 중합체를 19F-NMR, 1H-NMR, 및 GPC 측정한 바, 이하의 분석 결과가 되었다.The obtained white polymer was dissolved in 912 g of pure water, and the benzyl trimethylammonium salt was converted into a sulfonamide group using an ion exchange resin. When the obtained polymer was measured by 19 F-NMR, 1 H-NMR, and GPC, the following analysis results were obtained.

공중합 조성비(몰비) 모노머 1:메타크릴산 3,5-비스(헥사플루오로-2-하이드록시-2-프로필)사이클로헥실=0.8:0.2Copolymerization composition ratio (molar ratio) Monomer 1: methacrylic acid 3,5-bis (hexafluoro-2-hydroxy-2-propyl) cyclohexyl = 0.8: 0.2

중량 평균 분자량(Mw)=36,000Weight average molecular weight (Mw) = 36,000

분자량 분포(Mw/Mn)=1.88Molecular weight distribution (Mw/Mn)=1.88

이 고분자 화합물을 (폴리머 6)으로 한다.Let this high molecular compound be (Polymer 6).

Figure 112018017704619-pat00032
Figure 112018017704619-pat00032

[실시예 7][Example 7]

질소 분위기하, 64℃에서 교반한 메탄올 37.5g에, 모노머 1의 29.1g, 펜타플루오로스타이렌 3.9g과 2,2'-아조비스(아이소뷰티르산) 다이메틸 5.13g을 메탄올 112.5g에 녹인 용액을 4시간에 걸쳐 적하했다. 추가로 64℃에서 4시간 교반했다. 실온까지 냉각한 후, 1,000g의 아세트산 에틸에 격렬하게 교반하면서 적하했다. 생성된 고형물을 여과하여 취하고, 50℃에서 15시간 진공 건조하여, 백색 중합체 27.5g을 얻었다.In 37.5 g of methanol stirred at 64°C under a nitrogen atmosphere, 29.1 g of monomer 1, 3.9 g of pentafluorostyrene and 5.13 g of 2,2'-azobis(isobutyric acid) dimethyl were dissolved in 112.5 g of methanol. The solution was dripped over 4 hours. Furthermore, it stirred at 64 degreeC for 4 hours. After cooling to room temperature, it was dripped at 1,000 g of ethyl acetate, stirring vigorously. The resulting solid was collected by filtration and vacuum dried at 50°C for 15 hours to obtain 27.5 g of a white polymer.

얻어진 백색 중합체를 순수 912g에 용해하고, 이온 교환 수지를 이용하여 벤질트라이메틸암모늄염을 설폰아마이드기로 변환했다. 얻어진 중합체를 19F-NMR, 1H-NMR, 및 GPC 측정한 바, 이하의 분석 결과가 되었다.The obtained white polymer was dissolved in 912 g of pure water, and the benzyl trimethylammonium salt was converted into a sulfonamide group using an ion exchange resin. When the obtained polymer was measured by 19 F-NMR, 1 H-NMR, and GPC, the following analysis results were obtained.

공중합 조성비(몰비) 모노머 1:펜타플루오로스타이렌=0.8:0.2Copolymerization composition ratio (molar ratio) monomer 1: pentafluorostyrene = 0.8: 0.2

중량 평균 분자량(Mw)=36,000Weight average molecular weight (Mw) = 36,000

분자량 분포(Mw/Mn)=1.88Molecular weight distribution (Mw/Mn)=1.88

이 고분자 화합물을 (폴리머 7)로 한다.Let this high molecular compound be (Polymer 7).

Figure 112018017704619-pat00033
Figure 112018017704619-pat00033

[실시예 8][Example 8]

질소 분위기하, 64℃에서 교반한 메탄올 37.5g에, 모노머 1의 29.1g, 4-(헥사플루오로-2-하이드록시-2-프로필)스타이렌 5.4g과 2,2'-아조비스(아이소뷰티르산) 다이메틸 5.13g을 메탄올 112.5g에 녹인 용액을 4시간에 걸쳐 적하했다. 추가로 64℃에서 4시간 교반했다. 실온까지 냉각한 후, 1,000g의 아세트산 에틸에 격렬하게 교반하면서 적하했다. 생성된 고형물을 여과하여 취하고, 50℃에서 15시간 진공 건조하여, 백색 중합체 30.1g을 얻었다.In 37.5 g of methanol stirred at 64°C in a nitrogen atmosphere, 29.1 g of monomer 1, 5.4 g of 4-(hexafluoro-2-hydroxy-2-propyl) styrene and 2,2'-azobis(iso Butyric acid) A solution of 5.13 g of dimethyl dissolved in 112.5 g of methanol was added dropwise over 4 hours. Furthermore, it stirred at 64 degreeC for 4 hours. After cooling to room temperature, it was dripped at 1,000 g of ethyl acetate, stirring vigorously. The resulting solid was collected by filtration and vacuum dried at 50°C for 15 hours to obtain 30.1 g of a white polymer.

얻어진 백색 중합체를 순수 912g에 용해하고, 이온 교환 수지를 이용하여 벤질트라이메틸암모늄염을 설폰아마이드기로 변환했다. 얻어진 중합체를 19F-NMR, 1H-NMR, 및 GPC 측정한 바, 이하의 분석 결과가 되었다.The obtained white polymer was dissolved in 912 g of pure water, and the benzyl trimethylammonium salt was converted into a sulfonamide group using an ion exchange resin. When the obtained polymer was measured by 19 F-NMR, 1 H-NMR, and GPC, the following analysis results were obtained.

공중합 조성비(몰비) 모노머 1:4-(헥사플루오로-2-하이드록시-2-프로필)스타이렌=0.8:0.2Copolymerization composition ratio (molar ratio) Monomer 1:4- (hexafluoro-2-hydroxy-2-propyl) styrene = 0.8: 0.2

중량 평균 분자량(Mw)=32,000Weight average molecular weight (Mw) = 32,000

분자량 분포(Mw/Mn)=1.78Molecular weight distribution (Mw/Mn)=1.78

이 고분자 화합물을 (폴리머 8)로 한다.Let this high molecular compound be (Polymer 8).

Figure 112018017704619-pat00034
Figure 112018017704619-pat00034

전술한 바와 같이 하여 합성한 폴리머 1∼8은, 물, 메탄올, 에탄올, 아이소프로필알코올, 프로필렌 글라이콜 모노메틸 에터, 테트라하이드로퓨란, 다이메틸폼아마이드에 가용이었다.Polymers 1 to 8 synthesized as described above were soluble in water, methanol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether, tetrahydrofuran, and dimethylformamide.

이와 같이 본 발명의 제조 방법이면, 유기 용제에 가용이며, 특정한 강산의 설폰아마이드기를 갖는 본 발명의 도전성 폴리머용 고분자 화합물을 용이하게 제조할 수 있다.Thus, according to the manufacturing method of this invention, it is soluble in an organic solvent, and can manufacture easily the high molecular compound for conductive polymers of this invention which has the sulfonamide group of a specific strong acid.

한편, 본 발명은, 상기 실시형태로 한정되는 것은 아니다. 상기 실시형태는 예시이며, 본 발명의 특허청구의 범위에 기재된 기술적 사상과 실질적으로 동일한 구성을 갖고, 동일한 작용 효과를 발휘하는 것은, 어떠한 것이어도 본 발명의 기술적 범위에 포함된다.In addition, this invention is not limited to the said embodiment. The above-mentioned embodiment is an illustration, and any thing which has substantially the same structure as the technical idea described in the claim of this invention, and exhibits the same operation and effect is included in the technical scope of this invention.

Claims (5)

도전성 폴리머용의 도펀트로서,
하기 화학식(1)로 표시되는 반복 단위 a를 1종 이상 포함하고, 중량 평균 분자량이 1,000∼500,000의 범위인 것이고, 또한,
상기 도전성 폴리머용의 도펀트가, 추가로 하기 화학식(2)로 표시되는 반복 단위 b를 갖는 것인 것을 특징으로 하는 도전성 폴리머용의 도펀트.
Figure 112021020086711-pat00035

(식 중, R1은 수소 원자 또는 메틸기이고, Rf1은 탄소수 1∼4의 직쇄상, 분기상의 알킬기, 또는 페닐기이며, Rf1 중에 1개 이상의 불소 원자 또는 트라이플루오로메틸기를 갖는다. Z1은 단일 결합, 탄소수 6∼12의 아릴렌기, 또는 -C(=O)-O-R2-이고, R2는 탄소수 1∼12의 직쇄상, 분기상, 환상의 알킬렌기, 탄소수 6∼10의 아릴렌기, 또는 탄소수 2∼10의 알켄일렌기이며, R2 중에 에터기, 카보닐기, 에스터기를 갖고 있어도 된다. a는 반복 단위의 분자내 비율이고, 0＜a＜1.0이다.)
Figure 112021020086711-pat00042

(식 중, b는 반복 단위의 분자내 비율이고, 0＜b＜1.0이다.)As a dopant for a conductive polymer,
It contains at least one repeating unit a represented by the following formula (1) and has a weight average molecular weight in the range of 1,000 to 500,000, and
The dopant for a conductive polymer, wherein the dopant for the conductive polymer further has a repeating unit b represented by the following formula (2).
Figure 112021020086711-pat00035

(Wherein, R 1 is a hydrogen atom or a methyl group, Rf 1 is a linear or branched alkyl group having 1 to 4 carbon atoms, or a phenyl group, and has at least one fluorine atom or a trifluoromethyl group in Rf 1 . Z 1 is a single bond, an arylene group having 6 to 12 carbon atoms, or -C(=O)-OR 2 -, and R 2 is a linear, branched, cyclic alkylene group having 1 to 12 carbon atoms, aryl having 6 to 10 carbon atoms It is a lene group or an alkenylene group having 2 to 10 carbon atoms , and may have an ether group, a carbonyl group, or an ester group in R 2 , where a is the intramolecular ratio of the repeating unit, and 0<a<1.0.)
Figure 112021020086711-pat00042

(Wherein, b is the intramolecular ratio of the repeating unit, and 0<b<1.0.) 제 1 항에 있어서,
상기 화학식(1)로 표시되는 반복 단위 a가, 하기 화학식(3)으로 표시되는 반복 단위 a1∼a4로부터 선택되는 1종 이상을 포함하는 것인 것을 특징으로 하는 도전성 폴리머용의 도펀트.
Figure 112021020086711-pat00043

(식 중, R1 및 Rf1은 상기와 마찬가지이다. a1, a2, a3, 및 a4는 반복 단위의 분자내 비율이고, 0≤a1＜1.0, 0≤a2＜1.0, 0≤a3＜1.0, 0≤a4＜1.0, 0＜a1＋a2＋a3＋a4＜1.0이다.)The method of claim 1,
A dopant for a conductive polymer, wherein the repeating unit a represented by the formula (1) contains at least one selected from the repeating units a 1 to a 4 represented by the following formula (3).
Figure 112021020086711-pat00043

(Wherein, R 1 and Rf 1 are the same as above. a 1 , a 2 , a 3 , and a 4 are the intramolecular ratios of the repeating unit, 0≤a 1 <1.0, 0≤a 2 <1.0, 0≤a 3 <1.0, 0≤a 4 <1.0, 0 <a 1 +a 2 +a 3 +a 4 <1.0) 도전성 폴리머용의 도펀트의 제조 방법으로서,
카보닐기에 결합한 설폰아마이드기와 리튬, 나트륨, 칼륨, 또는 질소 화합물로 이루어지는 염의 구조를 갖는 모노머를 이용하여 중합 반응을 행하고, 중합 후, 이온 교환에 의해, 상기 카보닐기에 결합한 설폰아마이드기와 리튬, 나트륨, 칼륨, 또는 질소 화합물로 이루어지는 염의 구조를 카보닐기에 결합한 설폰아마이드기로 변환하는 것에 의해, 하기 화학식(1)로 표시되는 반복 단위 a를 포함하는 도전성 폴리머용의 도펀트를 제조하는 것을 특징으로 하는 도전성 폴리머용의 도펀트의 제조 방법.
Figure 112021020086711-pat00044

(식 중, R1은 수소 원자 또는 메틸기이고, Rf1은 탄소수 1∼4의 직쇄상, 분기상의 알킬기, 또는 페닐기이며, Rf1 중에 1개 이상의 불소 원자 또는 트라이플루오로메틸기를 갖는다. Z1은 단일 결합, 탄소수 6∼12의 아릴렌기, 또는 -C(=O)-O-R2-이고, R2는 탄소수 1∼12의 직쇄상, 분기상, 환상의 알킬렌기, 탄소수 6∼10의 아릴렌기, 또는 탄소수 2∼10의 알켄일렌기이며, R2 중에 에터기, 카보닐기, 에스터기를 갖고 있어도 된다. a는 반복 단위의 분자내 비율이고, 0＜a≤1.0이다.)A method for producing a dopant for a conductive polymer, the method comprising:
A polymerization reaction is carried out using a monomer having a salt structure consisting of a sulfonamide group bonded to a carbonyl group and lithium, sodium, potassium, or a nitrogen compound, and after polymerization, the sulfonamide group bonded to the carbonyl group is lithium, sodium by ion exchange. , potassium, or a dopant for a conductive polymer comprising a repeating unit a represented by the following formula (1) by converting the structure of a salt formed of a nitrogen compound into a sulfonamide group bonded to a carbonyl group. Conductivity characterized in that A method for producing a dopant for a polymer.
Figure 112021020086711-pat00044

(Wherein, R 1 is a hydrogen atom or a methyl group, Rf 1 is a linear or branched alkyl group having 1 to 4 carbon atoms, or a phenyl group, and has at least one fluorine atom or a trifluoromethyl group in Rf 1 . Z 1 is a single bond, an arylene group having 6 to 12 carbon atoms, or -C(=O)-OR 2 -, and R 2 is a linear, branched, cyclic alkylene group having 1 to 12 carbon atoms, aryl having 6 to 10 carbon atoms It is a lene group or an alkenylene group having 2 to 10 carbon atoms , and may have an ether group, a carbonyl group, or an ester group in R 2 , where a is the intramolecular ratio of the repeating unit, and 0<a≤1.0.) 제 3 항에 있어서,
상기 카보닐기에 결합한 설폰아마이드기와 리튬, 나트륨, 칼륨, 또는 질소 화합물로 이루어지는 염의 구조를 갖는 모노머를 이용하여 중합 반응을 행하여 얻어진 중합체가, 하기 화학식(4)로 표시되는 반복 단위를 포함하는 것인 것을 특징으로 하는 도전성 폴리머용의 도펀트의 제조 방법.
Figure 112021020086711-pat00045

(식 중, R1, Z1, Rf1, 및 a는 상기와 마찬가지이고, X는 리튬, 나트륨, 칼륨, 또는 하기 화학식(5)로 표시되는 질소 화합물이다.)
Figure 112021020086711-pat00046

(식 중, R101d, R101e, R101f, 및 R101g는, 각각 수소 원자, 혹은 탄소수 1∼12의 직쇄상, 분기상 또는 환상의 알킬기, 알켄일기, 옥소알킬기 또는 옥소알켄일기, 탄소수 6∼20의 아릴기, 또는 탄소수 7∼12의 아르알킬기 또는 아릴옥소알킬기를 나타내고, 이들 기의 수소 원자의 일부 또는 전부가 알콕시기에 의해 치환되어 있어도 된다. R101d와 R101e, R101d와 R101e와 R101f는 환을 형성해도 되고, 환을 형성하는 경우에는, R101d와 R101e 및 R101d와 R101e와 R101f는 탄소수 3∼10의 알킬렌기, 또는 식 중의 질소 원자를 환 중에 갖는 헤테로방향족환을 나타낸다.)
4. The method of claim 3,
A polymer obtained by carrying out a polymerization reaction using a monomer having a salt structure consisting of a sulfonamide group bonded to the carbonyl group and a lithium, sodium, potassium, or nitrogen compound contains a repeating unit represented by the following formula (4) A method for producing a dopant for a conductive polymer, characterized in that.
Figure 112021020086711-pat00045

(Wherein, R 1 , Z 1 , Rf 1 , and a are the same as above, and X is lithium, sodium, potassium, or a nitrogen compound represented by the following formula (5).)
Figure 112021020086711-pat00046

(Wherein, R 101d , R 101e , R 101f , and R 101g are each a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, and 6 carbon atoms represents an aryl group of -20, an aralkyl group of 7 to 12 carbon atoms, or an aryloxoalkyl group, and some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group.R 101d and R 101e , R 101d and R 101e and R 101f may form a ring, and in the case of forming a ring, R 101d and R 101e and R 101d and R 101e and R 101f are an alkylene group having 3 to 10 carbon atoms, or a heterocyclic group having a nitrogen atom in the ring. represents an aromatic ring.)
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